WO2017168066A1

WO2017168066A1 - Use of triarylbenzene derivatives as tracers for marking liquid fuels and motor fuels, liquid fuels and motor fuels containing such derivatives and corresponding processes

Info

Publication number: WO2017168066A1
Application number: PCT/FR2017/050517
Authority: WO
Inventors: Christophe Pays
Original assignee: Etablissements Steiner
Priority date: 2016-03-30
Filing date: 2017-03-09
Publication date: 2017-10-05
Also published as: FR3049614A1; FR3049614B1; EP3436552B1; EP3436552A1; ES2877166T3

Abstract

The present invention relates to the use, as tracer for marking liquid fuels and motor fuels, of at least one compound of Formula I; a liquid fuel or motor fuel containing at least one compound of Formula I; a process for marking liquid fuels or motor fuels, and processes for determining whether liquid fuels or motor fuels have been tampered with by whitening, by blending, or have been used illegally or have been the subject of smuggling or theft. Formula I in which the benzene ring A is optionally substituted in at least one of the positions 2, 4 or 6; and the benzene rings B, C and D are substituted, independently of one another, in at least one ortho, meta or para position relative to the benzene ring A.

Description

USE OF TRIARYLBENZENE DERIVATIVES AS MARKERS FOR MARKING FUELS AND LIQUID FUELS, FUELS AND LIQUID FUELS CONTAINING SUCH DERIVATIVES AND METHODS THEREOF

The present invention relates to the use of triarylbenzene derivatives as marking tracers for liquid fuels and fuels; liquid fuels and fuels containing such derivatives; a method of marking fuels and liquid fuels with such derivatives; and a method for determining whether liquid fuels initially containing these tracers have been tampered with, used illegally or stolen.

Marking fuels and liquid fuels with different types of chemical markers is well known in the art. Various compounds have been used for this purpose, as well as numerous analytical techniques for the detection of markers (for example, gas chromatography coupled with mass spectrometry). An important application is to mark combustible fuels according to their level of taxation. The deliberate removal of the tracer for illegal purposes is an important issue. Since tracers were dyes so far, "disposal methods" have been called "bleaching methods". These methods are physical (for example: adsorption on charcoal or on silica gel) or chemical (for example: acid or basic treatment). Therefore, these markers must be resistant to such disposal methods, be fully compatible with fuels liquids, and be identifiable by an appropriate analytical method.

Fraud involving fuels or liquid fuels covers various acts: falsification by bleaching or cutting, illegal use, contraband and theft. Laundering forgery concerns the conversion of low-tax fuel or liquid fuel into higher-taxed fuel or liquid fuel, for example - in France - the conversion of heating oil into diesel fuel. Falsification by cutting concerns the dilution of a high-rate fuel or liquid fuel by a low-tax fuel or liquid fuel. Illegal use refers to the illegal use of low-tax fuel or liquid fuel instead of higher-rate fuel or liquid fuel. Smuggling involves the purchase of low-tax fuel or liquid fuel in one country to resell it in another country where taxes are higher.

WO2012 / 153132 A1 discloses aromatic organic labels substituted with at least one bromine and / or one fluorine atom, and / or one or more fluoroalkyl groups. The combustion of fuels labeled with such compounds can produce hydrogen bromide and / or hydrogen fluoride in the flue gases. Bromide and hydrogen fluoride are known to be particularly corrosive to the engine. Hydrogen fluoride is well known to be highly toxic to people and the environment. WO2014 / 008164 discloses aryl and tritylated alkyl ethers as tracers for the labeling of hydrocarbons. Such tracers appear as not having good resistance to the abovementioned methods of elimination.

US 5,981,283 A discloses the use of a wide variety of organic compounds for the labeling of petroleum products including 1,3,5-triphenylbenzene. This tracer compound appears not to have good resistance to the abovementioned methods of elimination.

No. 7,858,373 describes the use of a variety of organic compounds for use in the labeling of liquid fuels such as hydrocarbons and oils. Combinations of markers can be used as digital marking systems, the ratio of the concentration of each marker forming a code of the labeled product.

There is therefore still a need for additional chemical markers compatible with liquid fuels and fuels, detectable in such a complex medium and resistant to physical and chemical bleaching methods, at least the physical method of bleaching with activated carbon and / or by silica.

Surprisingly, it has been discovered that certain triarylbenzenes are particularly effective for the marking of liquid fuels and fuels. In addition, it has been shown that these triarylbenzenes are particularly resistant to bleaching attempts chemical and physical. In addition, most of these triarylbenzenes contain only carbon and hydrogen, and the burning of these compounds used as markers produces only carbon dioxide and water.

The present invention therefore firstly relates to the use as marker tracer of fuels and liquid fuels of at least one compound of Formula I:

Formula I in which:

the benzene ring A is optionally substituted in at least one of the 2, 4 or 6 positions by:

A linear, branched or cyclic C1-C18 alkyl radical, optionally substituted with at least one halogen and / or optionally interrupted by at least one oxygen; or

An alkoxy radical, linear, branched or cyclic, Ci-Cis, optionally substituted with at least one halogen and / or optionally interrupted by at least one oxygen; or

A C ₂ -C 18 linear, branched or cyclic alkenyl radical, optionally substituted with at least one halogen and / or optionally interrupted by at least one oxygen; the benzene rings B, C and D are substituted, independently of one another, in at least one ortho, meta or para position relative to the benzene ring A by:

An alkyl radical, linear, branched or cyclic, in

Ci - Cis, optionally substituted by at least one halogen and / or optionally interrupted by at least one oxygen; or

• an alkenyl radical, linear, branched or cyclic C ₂ - Ci _8, optionally substituted by at least one halogen and / or optionally interrupted by at least one oxygen; or

• a halogen;

at least one benzene ring B, C and D may also comprise a 5-7 membered aliphatic ring attached to it, for example a 6-membered ring,

with the proviso that when the benzene ring A is unsubstituted and the benzene rings B, C and D are each substituted by methyl, the latter is not in the para position with respect to the benzene ring A.

Note that in Formula 1 any atom can be replaced by one of its isotopes. Preferably, the benzene ring A is unsubstituted or substituted by alkoxy - Ci _8. Preferably, the benzene rings B, C and D are substituted with:

an alkyl radical, linear, branched or cyclic, Ci-Cis, especially C ₁ -C ₁₂ , in particular Ci-C ₆ , optionally substituted by at least one halogen; or at least one halogen.

Halogen falling within the definition of Formula I may be F, Cl, Br and I, and especially F, Cl and Br.

The compound of formula I may especially be chosen from:

In a particularly preferred manner, the compound Formula I is:

The invention also relates to a fuel or liquid fuel containing as tracer label at least one compound of Formula I.

As fuel or liquid fuel, we can b:

liquid fuels or fuels obtained from petroleum, among which mention may be made of gasoline, diesel fuel, domestic fuel oil, kerosene, kerosene;

liquid fuels or fuels obtained from plants such as biofuels, among which mention may be made of vegetable oils, ethanol, butanol, ethyl tert-butyl ether (ETBE), methyl esters of fatty acid.

The compounds of Formula I can be prepared by palladium-catalyzed Suzuki coupling between a 1,3,5-trihalogenoarene optionally substituted at the 2, 4 or 6 positions and three equivalents of an arylboronic acid in the presence of a mineral base:

The compounds of Formula I not being substituted on the benzene ring A can also be prepared by cyclotrimerization of aryl methyl ketones according to:

The reaction takes place at 80 to 150 ° C in the presence of catalysts or desiccants. The catalysts are Bronsted or Lewis acids. The use of arenesulphonic acids is well described in the literature. In particular, the use of a catalytic amount of 4-toluenesulfonic acid monohydrate is described in Zhao, Y .; Li, J.; Li, C.; Yin, K.; Ye, D.; Jia, X. Green Chem. 2010, 12, 1370.

The compound of formula I can be added to the fuel or liquid fuel at a rate of 0.01 to 500 mg / l, in particular at a rate of 0.02 to 20 mg / l, and more particularly at a level of 0.1 to 5 mg / L.

The subject of the invention is also a process for marking liquid fuels or fuels, characterized in that a 0.1 to 40% by weight solution of the compound of Formula I is prepared in a solvent or a mixture of solvents. and that said solution is injected into the fuel or liquid fuel for example in line in a pipeline or the loading arm of a tanker truck, or in a tank to obtain the target concentration of the marker in the fuel or liquid fuel. Preferably, a 0.2 to 20% by weight solution of the compound of Formula I is prepared in the solvent or solvent mixture. The solvent or solvents may be chosen from aromatic solvents such as toluene, ethylbenzene, xylenes, mesitylene, 1,2,4-trimethylbenzene, cumene, p-cymene and aromatic hydrocarbons (for example Shellsol). ^® A100, Solvarex ^® 10, Solvesso ^® 200); among aliphatic solvents such as pentane, hexanes, cyclohexane, heptanes, 2,2,4-trimethylpentane, white spirits, kerosene, isoparaffins, paraffins; among oxygenated and / or nitrogenous solvents such as ketones, ethers, esters, lactones, phenols, amides, lactams; or from halogenated solvents such as chlorobenzene, 1,2-dichlorobenzene, 1 ', α, α, α-trifluorotoluene.

The invention also relates to a method for determining whether liquid fuels have been falsified by bleaching, characterized in that a sample of the fuel or liquid fuel suspected to have been tampered with and it is analyzed to determine if the concentration of the compound of Formula I in said sample is lower than the initial concentration, and if so, it is deduced that the sample has been falsified by bleaching.

The invention also relates to a method for determining whether liquid fuels have been falsified by cutting, or have been used illegally or have been smuggled or stolen, characterized by the fact that take a sample of fuel or liquid fuel suspected to have been falsified or illegally used or smuggled or stolen, and analyzed for the presence of the compound of Formula I in the sample, and, if so, it can be concluded that the sample was falsified or used illegally or is smuggled or stolen.

It may be emphasized here that the marker (s) according to the invention can be used individually or in combination with other markers.

The liquid fuels or fuels labeled with one or more compounds of Formula I can be analyzed qualitatively or quantitatively, for example by the following methods: gas chromatography coupled to a flame ionization detector or a mass spectrometer; high performance liquid chromatography coupled to a diode array detector or mass spectrometer.

The following Examples illustrate the present invention without however limiting its scope. In these Examples, the percentages are by weight unless otherwise indicated.

The following tests for physical and chemical removal of the markers were carried out on the compounds of Examples 1 (reference), 2 to 18 (of the invention) and 19 and 20 (comparative). Physical elimination test

In a test tube, 10 mL of B0 type gas oil according to EN 590 containing 10 mg / L of chemical marker was added a quantity - specified in the rest of the text - of solid elimination agent: gel silica ¹ , activated carbon ² , alumina ³ .

The tube was stirred using a linear stirrer at 300 motions / min for 10 min.

The liquid was then filtered through a 0.2 μπι polytetrafluoroethylene (PTFE) membrane and analyzed by GC / FID.

Column ZB-50 of 15 m × 0.25 mm × 0.25 μπι ID.

Helium P = 90kPa

Flow of 50 mL / min.

Injector 280 ° C

300 ° C detector

Oven: 100 ° C to 320 ° C at 20 ° C / min then 320 ° C for 19 min.

Volume injected: 2 μL.

Chemical elimination test

In a test tube, 10 mL of B0 type gas oil according to EN 590 containing 10 mg / L of chemical marker was added 10 mL of chemical removal agent: H ₂ SO ₄ , HNO ₃ , NaOH , NaC10, HC1 at the indicated concentrations.

The tube was stirred using a linear stirrer at 300 motions / min for 10 min. After a few minutes of rest, the liquid constituting the phase

¹ 0.060 - 0.200 mm, 40A, Acros 241660010

² Comelt Carbosorb 10A

³ Sigma-Aldrich 11028 The upper part was removed and then filtered through a 0.45 μπι polytetrafluoroethylene (PTFE) membrane and analyzed by GC / FID. The analysis conditions are those indicated above for the physical elimination test.

Diesel fuel containing the compound of Examples 1 to

18 at the concentration of 10 mg / L was subjected to the physical and chemical elimination tests described above. The concentration of each compound, measured in the gas oil after the removal treatment, is shown in Tables 1 to 18 respectively as a percentage of the concentration measured before the removal treatment.

Example 1 (reference): 1, 3, 5-Tris (4-methylphenyl) benzene

A mixture of 134.2 g of 4'-methylacetophenone and 19 g of 4-toluenesulphonic acid monohydrate was heated to 140 ° C with stirring. The water was distilled off to reach the temperature and then during the course of the reaction. The temperature of 140 ° C was maintained for 24 hours.

After cooling the reaction mixture to room temperature, toluene was added to dissolve the mass. The organic solution was then washed 3 times with water and then dried with magnesium sulfate. The solvent was distilled off in vacuo. 92 g of 1,3,5-tri (4-methylphenyl) enzene was obtained. Purification by silica gel chromatography (cyclohexane / ethyl acetate: 99/1) followed by recrystallization from ethanol gave a beige crystalline powder.

Table 1

For 10 ml of marked diesel:

Example 2 (of the invention)

isobutylphenyl) benzene

The title compound was prepared according to the procedure of Example 1 except that the starting mixture was a mixture of 176.3 g of 4'-isobutylacetophenone and 19 g of 4-toluenesulfonic acid monohydrate.

126 g of a highly viscous brown liquid containing 68% (w / w) of 1, 3, 5-tri (4-isobutylphenyl) benzene was obtained. Table 2

For 10 ml of marked diesel:

Example 3 (of the invention)

butylphenyl) benzene

The title compound was prepared according to the procedure of Example 1 except that the starting mixture was a mixture of 10 g of 4'-butylacetophenone and 1.1 g of 4-toluenesulfonic acid monohydrate.

10.1 g of 1,3,5-tri (4-butylphenyl) benzene was obtained as a highly viscous brown liquid.

Table 3

For 10 ml of marked diesel

Silica Silica Coal H ₂ S0 ₄ to HNO ₃ to

0.5g 2g active 95% 65%

ig

100% 86% 63% 112% 83% Example 4 (of the invention) 1,3,5-Tris (4-tert-butylphenyl) enzene

1.23 g of 1,3,5-triphenylbenzene was suspended in 10 ml of dichloromethane and 1.5 ml of 2-chloro-2-methylpropane. 25 mg of ferric chloride were then added. After a few minutes, water and dichloromethane were added with stirring. The organic solution was then washed twice with 10% aqueous sodium carbonate solution, dried with magnesium sulfate and evaporated in vacuo. 1.88 g of 1,3,5-tris (4-tert-butylphenyl) benzene was obtained. A white crystalline product was obtained after recrystallization from toluene.

Table 4

For 10 ml of marked diesel:

Silica Silica Activated Carbon H ₂ S0 ₄ 0, 5g 2g ig 95%

96% 61% 99% 83% Example 5 (of the invention)

ethylene (benzene) benzene

The title compound was prepared according to the procedure of Example 1 except that the starting mixture was a mixture of 10 g of 4'-ethylacetophenone and 1.3 g of 4-toluenesulphonic acid monohydrate.

7.3 g of 1,3,5-tris (4-ethylphenyl) benzene was obtained as a highly viscous brown liquid.

Table 5

For 10 ml of marked diesel:

Example 6 (of the invention): 1, 3, 5-Tris (4-fluorophenyl) benzene

Under an argon atmosphere, a mixture of 630 mg of 1,3,5-tribromobenzene, 1,007 g of 4-fluorophenylboronic acid, 15 mg of palladium acetate and 52 mg of triphenylphosphine in 4 mL of aqueous sodium carbonate solution. 2M sodium and 13 mL of 1-propanol was refluxed with stirring for 3 h.

20 mL of water was then added. The product was extracted twice with ethyl acetate. The organic solution was then washed with aqueous sodium bicarbonate 4% and with saturated brine, dried over magnesium sulfate, filtered through Hyflo ^® and evaporated in vacuo. The crude product was recrystallized from ethanol to give 0.53 g of 1,3,5-tris (4-fluorophenyl) benzene as a greyish white crystalline powder.

Table 6

For 10 ml of marked diesel:

Example 7 (of the invention)

chlorophenyl) benzene

1,3,5-Tri (4-chlorophenyl) enzene was prepared according to the procedure of Example 1, replacing 4'-methylacetophenone with 4'-chloroacetophenone. The crude product was recrystallized from ethanol. 36.8 g of yellowish-white crystals were obtained.

Table 7

For 10 ml of marked diesel:

Example 8 (of the invention)

bromophenyl) benzene

1,3,5-Tri (4-bromophenyl) benzene was prepared according to the procedure of Example 1, replacing 4'-methylacetophenone with 4'-bromoacetophenone. The crude product was recrystallized from toluene. 54.3 g of yellowish-white crystals were obtained. Table 8

For 10 ml of marked diesel:

Example 9 (of the invention): 1-Dodecyloxy-2,4,6-tris (4-fluorophenyl) benzene

A mixture of 12.8 g of 2, 4, 6 -tribromophenol,

9.85 g of 1-bromododecane and 10.35 g of potassium carbonate in 25 ml of N-ethylpyrrolidone was heated at 115 ° C with stirring for 2 h. The mixture was then poured into cold water. 16% hydrochloric acid was added until pH <2. The product was then extracted with cyclohexane. The organic solution was then washed with water, dried over potassium carbonate and evaporated in vacuo to give 18.6 g of 1-dodecyloxy-2,4,6-tribromobenzene.

Under an argon atmosphere, a mixture of 998 mg of 1-dodecyloxy-2,4,6-tribromobenzene, 1.007 g of 4-fluorophenylboronic acid, 15 mg of palladium acetate and 52 mg of triphenylphosphine in 4 mL of solution. aqueous solution of 2M sodium carbonate and 13 mL of 1-propanol was heated at reflux temperature with stirring for 3 h.

20 mL of water was then added. The product was extracted twice with ethyl acetate. The organic solution was then washed with aqueous sodium bicarbonate 4% and with saturated brine, dried over magnesium sulfate, filtered through Hyflo ^® and evaporated in vacuo. The crude product was recrystallized from ethanol to give 0.69 g of 1-dodecyloxy-2,4,6-tris (4-fluorophenyl) benzene as a white crystalline powder.

Table 9

For 10 ml of marked diesel:

Example 10 (of the invention): 1-O-oxyoxy-2,4,6-tris (4-fluorophenyl) benzene

1-Octyloxy-2,4,6-tribromobenzene was prepared following the procedure of Example 9 substituting 1-bromooctane for 1-bromododecane.

Under argon atmosphere, a mixture of 1.33 g of 1-octyloxy-2,4,6-tribromobenzene, 1.51 g of 4- fluorophenylboronic acid, 99 mg of palladium acetate and 297 mg of triphenylphosphine in 6 mL of 2M aqueous sodium carbonate solution and 20 mL of 1-propanol was refluxed with stirring for 2 h.

20 mL of water was then added. The product was extracted twice with ethyl acetate. The organic solution was then washed with aqueous sodium bicarbonate 4% and with saturated brine, dried over magnesium sulfate, filtered through Hyflo ^® and evaporated in vacuo. The crude product was recrystallized from ethanol to give 0.4 g of 1-octyloxy-2,4,6-tris (4-fluorophenyl) benzene as a white crystalline powder.

Table 10

For 10 ml of marked diesel:

Example 11 (of the invention): 1-Butoxy-2,4,6-tris (4-fluorophenyl) benzene

1-Butoxy-2,4,6-tribromobenzene was prepared according to the procedure of Example 9 substituting 1-bromobutane for 1-bromododecane. Under an argon atmosphere, a mixture of 774 mg of 1-butoxy-2,4,6-tribromobenzene, 1.007 g of 4-fluorophenylboronic acid, 15 mg of palladium acetate and 52 mg of triphenylphosphine in 4 mL of an aqueous solution of 2M sodium carbonate and 13 mL of 1-propanol was refluxed with stirring for 2 h.

20 mL of water was then added. The product was extracted twice with ethyl acetate. The organic solution was then washed with aqueous sodium bicarbonate 4% and with saturated brine, dried over magnesium sulfate, filtered through Hyflo ^® and evaporated in vacuo. The crude product was recrystallized from ethanol to give 0.52 g of 1-butoxy-2,4,6-tris (4-fluorophenyl) benzene as a white crystalline powder.

Table 11

For 10 ml of marked diesel:

Example 12 (of the invention): 1-Dodecyloxy-2,4,6-tris (3,4-difluorophenyl) benzene

Under an argon atmosphere, a mixture of 998 mg of 2,4-dodecyloxy-2,4,6-tribromobenzene (see Example 9), 1.14 g of 3,4-difluorophenylboronic acid, 66 mg of palladium acetate and 200 mg of triphenylphosphine in 4 mL of 2M aqueous sodium carbonate solution and 13 mL of 1-propanol was refluxed with stirring for 2 h.

20 mL of water was then added. The product was extracted twice with ethyl acetate. The organic solution was then washed with aqueous sodium bicarbonate 4% and with saturated brine, dried over magnesium sulfate, filtered through Hyflo ^® and evaporated in vacuo. The crude product was recrystallized from ethanol to give 0.48 g of 1-dodecyloxy-2,4,6-tris (3,4-difluorophenyl) benzene as a white crystalline powder.

Table 12

For 10 ml of marked diesel:

Example 13 (of the invention): 1 -Octyloxy-2,4,6-tris (3,4-difluorophenyl) benzene

Under argon atmosphere, a mixture of 886 mg of 1-octyloxy-2,4,6-tribromobenzene (see Example 10), 1.14 g of 3,4-difluorophenylboronic acid, 15 mg of palladium acetate and 52 mg of triphenylphosphine in 4 mL of 2 M aqueous sodium carbonate solution and 13 mL of 1-propanol was refluxed with stirring for 3 h.

20 mL of water was then added. The product was extracted twice with ethyl acetate. The organic solution was then washed with aqueous sodium bicarbonate 4% and with saturated brine, dried over magnesium sulfate, filtered through Hyflo ^® and evaporated in vacuo. The crude product was recrystallized from ethanol to give 0.83 g of 1-octyloxy-2,4,6-tris (3,4-difluorophenyl) benzene as a greyish crystalline powder.

Table 13

For 10 ml of marked diesel:

Example 14 (of the invention): 1-Dodecyloxy-2,4,6-tris (4-methylphenyl) benzene

Under argon atmosphere, a mixture of 998 mg of 2,4-dodecyloxy-4,6-tribromobenzene (see Example 9), 979 mg of 4-tolylboronic acid, 66 mg of palladium acetate and 199 mg of triphenylphosphine in 4 mL of 2M aqueous sodium carbonate solution and 14 mL of 1-propanol was refluxed with stirring for 4 h. 20 mL of water was then added. The product was extracted twice with ethyl acetate. The organic solution was then washed with aqueous sodium bicarbonate 4% and with saturated brine, dried over magnesium sulfate, filtered through Hyflo ^® and evaporated in vacuo. The crude product was recrystallized from ethanol to give 0.59 g of 1-octyloxy-2,4,6-tris (4-methylphenyl) benzene is obtained as a white crystalline powder.

Table 14

For 10 ml of marked diesel:

Example 15 (of the invention): 1-Oxytyloxy-2,4,6-tris (4-methylphenyl) benzene

Under argon atmosphere, a mixture of 886 mg of 1-octyloxy-2,4,6-tribromobenzene (see Example 10), 979 mg of 4-tolylboronic acid, 66 mg of palladium acetate and 199 mg of triphenylphosphine in 4 mL of 2M aqueous sodium carbonate solution and 14 mL of 1-propanol was refluxed with stirring for 2 h.

20 mL of water was then added. The product was extracted twice with ethyl acetate. The organic solution was then washed with aqueous sodium bicarbonate 4% and with saturated brine, dried over magnesium sulfate, filtered through Hyflo ^® and evaporated in vacuo. The crude product was recrystallized from ethanol to give 0.58 g of 1-octyloxy-2,4,6-tris (4-methylphenyl) benzene as a white crystalline powder.

Table 15

For 10 ml of marked diesel:

Example 16 (of the invention): 1-Butoxy-2,4,6-tris (4-methylphenyl) benzene

Under an argon atmosphere, a mixture of 182 mg of 1-butoxy-2,4,6-tribromobenzene (see Example 11), 230 mg of 4-tolylboronic acid, 15 mg of palladium acetate and 47 mg of triphenylphosphine in 1 mL of 2M aqueous sodium carbonate solution and 3.5 mL of 1-propanol was refluxed with stirring for 2 h.

20 mL of water was then added. The product was extracted twice with ethyl acetate. The organic solution was then washed with aqueous sodium bicarbonate 4% and with saturated brine, dried over magnesium sulfate, filtered through Hyflo ^® and evaporated in vacuo. The crude product was recrystallized from ethanol to give 0.15 g of 1-octyloxy-2,4,6-tris (4-methylphenyl) benzene as a white crystalline powder.

Table 16

For 10 ml of marked diesel:

Example 17 (of the invention)

trifluoromethyl-phenyl) benzene

Under an argon atmosphere, a mixture of 998 mg of 1-dodecyloxy-2,4,6-tribromobenzene (see Example 9), 1.37 g of 3-trifluoromethylphenylboronic acid, 66 mg of palladium acetate and 199 mg triphenylphosphine in 4 mL of 2M aqueous sodium carbonate solution and 14 mL of 1-propanol was refluxed with stirring for 3 h.

20 mL of water was then added. The product was extracted twice with ethyl acetate. The organic solution was then washed with aqueous sodium bicarbonate 4% and with saturated brine, dried over magnesium sulfate, filtered through Hyflo ^® and evaporated in vacuo. 1.62 g of 1-dodecyloxy-2,4,6-tris (3-trifluoromethylphenyl) benzene as a brownish oil.

Table 17

For 10 ml of marked diesel:

Example 18 (of the invention)

methylphenyl) benzene

The product is marketed by Sigma-Aldrich (ref 764671.

Table 18

For 10 ml of marked diesel

Example 19 (Comparative): ((3- (sec-Butyl) -4-

(decyloxy) phenyl) methanetriyl) tribenzene

Patent application WO2014 / 008164 describes in particular the ((3- (sec-butyl) -4- (decyloxy) phenyl) méthanetriyl) tribenzène, sold under the name ^® Accutrace S10.

Gas oil containing (3- (sec-butyl) -4- (decyloxy) phenyl) methanetriyl) tribenzene at a concentration of 10 mg / L was subjected to the physical and chemical elimination tests described above. The concentration of the compound measured in the gas oil after the removal treatment is shown in Table 19 as the percentage of the concentration measured before the removal treatment. Table 19

For 10 ml of marked diesel:

The compound of Example 2 is significantly more resistant to silica treatment than the compound of Comparative Example 19. Moreover, the marker of Comparative Example 19 is completely removed by nitric acid while the compound of Example 2 shows very good resistance to this chemical agent.

Example 20 (Comparative): 1, 3, 5-Triphenylbenzene (TPB)

The product is marketed by Sigma-Aldrich (ref.

T82007).

Table 20

For 10 ml of marked diesel

The compound of Example 2 is significantly more resistant to treatment with activated carbon than TPB. In addition, the compound of Example 2 is superior to TPB for resistance to treatment with silica. EXAMPLE 21 Test for Clogging Fuel Injection Nozzles According to the CEC Standard F-23-01 This test was conducted on B0 type gas oil according to the EN 590 standard on the one hand without marker and on the other hand with the marker of Example 2 added at a rate of 6.8 mg / L.

The average percentage reduction of the airflow in the injector at 0.1 mm needle lift is 70.8 for the unlabeled fuel and 69.5 for the marker fuel. The addition of the marker therefore has no significant influence on the fouling of the injection nozzles.

Claims

1 - Use as marking tracer of fuels and liquid fuels of at least one compound of Formula I:

Formula I in which:

A linear, branched or cyclic C1-C18 alkyl radical, optionally substituted by at least one halogen and / or optionally interrupted by at least one oxygen; or

• an alkoxy radical, linear, branched or cyclic Ci-Ci _8, optionally substituted by at least one halogen and / or optionally interrupted by at least one oxygen; or

A C ₂ -C 18 linear, branched or cyclic alkenyl radical, optionally substituted by at least one halogen and / or optionally interrupted by at least one oxygen;

the benzene rings B, C and D are substituted, independently of one another, in at least one ortho, meta or para position relative to the benzene ring A by: A linear, branched or cyclic C 1 -C 18 alkyl radical, optionally substituted by at least one halogen and / or optionally interrupted by at least one oxygen; or

A linear, branched or cyclic C1-C18 alkoxy radical, optionally substituted by at least one halogen and / or optionally interrupted by at least one oxygen; or

A C ₂ -C 18 linear, branched or cyclic alkenyl radical, optionally substituted by at least one halogen and / or optionally interrupted by at least one oxygen; or

• a halogen;

at least one benzene ring B, C and D may also comprise a 5-7 membered aliphatic ring attached thereto,

2 - The use according to claim 1, characterized in that the benzene ring A is unsubstituted or substituted by alkoxy-Ci _8.

3 - Use according to one of claims 1 and 2, characterized in that the benzene rings B, C and D are substituted by:

a linear, branched or cyclic C 1 -C 18, especially C ₁ -C 12, in particular C ₁ -C ₆ , alkyl radical, optionally substituted with at least one halogen; or at least one halogen. 4 - Use according to one of claims 1 to 3, characterized in that a halogen falling within the definition of Formula I is F, Cl, Br and I, and in particular F, Cl and Br.

5 - Use according to one of claims 1 to 4, characterized in that the compound of formula I is chosen from:

in particular

6 - Fuel or liquid fuel containing as marker tracer at least one compound of Formula I as defined in one of claims 1 to 5. 7 - Fuel or liquid fuel according to claim 6, characterized in that the compound of Formula I is added to the fuel or liquid fuel at a rate of 0.01 to 500 mg / l, in particular at a rate of 0.02 to 20 mg / l, and more particularly at a rate of 0.1 to 5 mg / l.

8 - Method for marking liquid fuels or fuels, characterized in that a 0.1 - 40% by weight solution of the compound of formula I as defined in one of claims 1 to 5 is prepared in a solvent or a mixture of solvents and that said solution is injected into the fuel or liquid fuel for example in line in a pipeline or the loading arm of a tanker truck, or even in a tank to obtain the concentration aiming the marker in the fuel or liquid fuel.

9 - Process according to claim 8, characterized in that a 0.2 to 20% by weight solution of the compound of formula I is prepared in the solvent or solvent mixture.

10 - Process according to one of claims 8 and 9, characterized in that the solvent or solvents are chosen from aromatic solvents such as toluene, ethylbenzene, xylenes, mesitylene, 1,2,4- trimethylbenzene, cumene, p-cymene, aromatic hydrocarbons (eg Shellsol ^® A100, Solvarex ^® 10, Solvesso ^® 200); among aliphatic solvents such as pentane, hexanes, cyclohexane, heptanes, 2,2,4-trimethylpentane, white spirits, kerosene, isoparaffins, paraffins; among oxygenated and / or nitrogenous solvents such as ketones, ethers, esters, lactones, phenols, amides, lactams; or from halogenated solvents such as chlorobenzene, 1,2-dichlorobenzene, 1 ', α, α, α-trifluorotoluene. 11 - Method for determining whether liquid fuels have been falsified by bleaching, characterized in that a sample of the fuel or liquid fuel suspected to have been falsified is taken and analyzed for determining whether the concentration of the compound of formula I as defined in one of claims 1 to 5 in said sample is lower than the initial concentration, and if so, it is deduced that the sample has been falsified by bleaching .

12 - Method for determining whether liquid fuels have been falsified by cutting, or have been used illegally or have been smuggled or stolen, characterized in that a sample of the fuel or liquid fuel suspected to have been falsified or used illegally or being smuggled or stolen, and analyzed for the purpose of determining whether the compound of Formula I as defined in any of claims 1 to 5 is present in said sample, and if so, it is deduced that the sample has been falsified or used illegally or is smuggled or stolen.